BACKGROUND OF THE INVENTION
[0001] Described herein are methods for making organoaminosilane compounds that may be useful,
for example, as chemical precursor for depositing a silicon-containing film. Also
described herein are compounds, more specifically organoamine, organoaminosilane,
organoaminodisilane, and/or organoaminocarbosilane compounds, that are suitable for
use in a variety of industrial applications.
[0002] Organoaminosilanes containing the -SiH
3 or -SiH
2- moieties are desirable precursors for the deposition of silicon-containing films
such as, without limitation, silicon oxide and silicon nitride films or doped versions
thereof. For example, volatile compounds such as without limitation organoaminosilanes,
organoaminodisilanes, and/or organoaminocarbosilanes are important precursors used
for the deposition of silicon-containing films in the manufacture of semiconductor
devices. One particular embodiment of an organoaminosilane compound is di-iso-propylaminosilane
(DIPAS), which has previously been shown to exhibit desirable physical properties
for the controlled deposition of such films. Although DIPAS can be prepared by the
direct reaction of di-iso-propylamine (DIPA) or lithium-di-iso-propylamide with monochlorosilane
(MCS) or monochlorodisilane (MCDS), MCS or MCDS is not an abundant commodity chemical
and is therefore subject to limited availability and price instability. Furthermore,
synthesis of organoaminosilanes using MCS may produce stoichiometric amounts of amine
hydrochloride salts that can be highly absorbent thereby complicating recovery of
organoaminosilane products.
[0003] The prior art describes some methods for the production of organoaminosilane compounds.
Japanese Patent
JP49-1106732 describes a method for preparing silylamines by the reaction of an imine and a hydridosilane
in the presence of a rhodium (Rh) complex. Exemplary silylamines that were prepared
include: PhCH
2N(Me)SiEt
3, PhCH
2N(Me)SiHPh
2, PhCH
2N(Ph)SiEt
3, and PhMeCHN(Ph)SiHEt
2 wherein "Ph" means phenyl, "Me" means methyl, and "Et" means ethyl.
[0004] U.S. Pat. No. 6,072,085 describes a method for preparing a secondary amine from a reaction mixture comprising
an imine, a nucleophilic activator, a silane, and a metal catalyst. The catalyst acts
to catalyze the reduction of the imine by a hydrosilylation reaction.
[0005] U.S. Pat. No. 6,963,003, which is owned by the assignee of the present application, provides a method for
preparing an organoaminosilane compound comprising reacting a stoichiometric excess
of at least one amine selected from the group consisting of secondary amines having
the formula R
1R
2NH, primary amines having the formula R
2NH
2 or combinations thereof with at least one chlorosilane having the formula R
3nSiCl
4-n under anhydrous conditions sufficient such that a liquid comprising the aminosilane
product and an amine hydrochloride salt is produced wherein R
1 and R
2 can each independently be a linear, cyclic or branched alkyl group having 1 to 20
carbon atoms; R
3 can be a hydrogen atom, an amine group, or a linear, cyclic or branched alkyl group
having 1 to 20 carbon atoms; and n is a number ranging from 1 to 3.
[0006] U. S. Pat. No. 7,875,556, which is owned by the assignee of the present application, describes a method for
making an organoaminosilane by reacting an acid with an arylsilane in the presence
of a solvent, adding a secondary amine and tertiary amine, and removing the reaction
byproduct using phase separation and the solvent using distillation.
[0007] U.S. Publ. No. 2012/0277457, which is owned by the assignee of the present application, describes a method for
making an organoaminosilane compound having the following formula:
H
3SiNR
1R
2
wherein R
1 and R
2 are each independently selected from C
1-C
10 linear, branched or cyclic, saturated or unsaturated, aromatic, heterocyclic, substituted
or unsubstituted alkyl groups wherein R
1 and R
2 are linked to form a cyclic group or wherein R
1 and R
2 are not linked to form a cyclic group comprising the steps of: reacting a halosilane
having the formula H
nSiX
4-n wherein n is 0, 1, or 2 and X is Cl, Br, or a mixture of Cl and Br, with an amine
to provide a slurry comprising a haloaminosilane compound X
4-nH
n-1SiNR
1R
2 wherein n is a number selected from 1, 2 and 3; and X is a halogen selected from
CI, Br, or a mixture of Cl and Br; and introducing into the slurry a reducing agent
wherein at least a portion of the reducing agent reacts with the haloaminosilane compound
and provides an end product mixture comprising the aminosilane compound.
[0008] Korean Patent No.
10-1040325 provides a method for preparing an alkylaminosilane which involves reacting a secondary
amine and trichloroalkylsilane in an anhydrous atmosphere and in the presence of a
solvent to form an alkyl aminochlorosilane intermediate and a metal hydride LiAlH
4 is added to the alkyl aminochlorosilane intermediate as a reducing agent to form
the alkylaminosilane. The alkylaminosilane is then subjected to a distillation process
to separate and purify the alkylaminosilane.
[0009] Reference article entitled "
Homogeneous Catalytic Hydrosilylation of Pyridines", L. Hao et al., Angew. Chem.,
Int. Ed., Vol. 37, 1998, pp. 3126-29 describes the hydrosilylation of pyridines, e.g. RC
5H
4N (R = H, 3-Me, 4-Me, 3-CO
2Et), by PhSiH
2Me, Ph
2SiH
2 and PhSiH
3 in the presence of a titanocene complex catalyst such as a [Cp
2TiMe
2], which provided high yields of 1-silylated tetrahydropyridine derivatives and the
intermediate silyltitanocene adduct, Cp
2Ti(SiHMePh)(C
5H
5N) (I).
[0010] Reference article entitled "
Stoichiometric Hydrosilylation of Nitriles and Catalytic Hydrosilylation of Imines
and Ketones Using a µ-Silane Diruthenium Complex", H. Hashimoto et al., Organometallics,
Vol. 22, 2003, pp. 2199-2201 describes a method to synthesize µ-iminosilyl complexes Ru
2(CO)
4(µ-dppm)(µ-SiToI
2)(µ-RCH:NSiToI
2) (R = Me, Ph, t-Bu, CH:CH
2) in high yields during the stoichiometric reactions of a diruthenium complex having
Ru-H-Si interactions, {Ru(CO)
2(SiToI
2H)}
2(µ-dppm)(µ-η
2:η
2-H
2SiToI
2), with nitriles RCN.
[0011] Reference article entitled "
Titanocene-Catalyzed Hydrosilylation of Imines: Experimental and Computational Investigations
of the Catalytically Active Species", H. Gruber-Woelfler et al., Organometallics,
Vol. 28, 2009, pp. 2546-2553 described the asymmetrical catalytic hydrosilylation of imines using (R,R)-ethylene-1,2-bis(n
5-4,5,6,7-tetrahydro-1-indenyl)titanium (R)-1,1'-binaphth-2-olate (1) and (S,S)-ethylene-1,2-bis(η
5-4,5,6,7-tetrahydro-1-indenyl)titanium dichloride (2) as catalyst precursors. After
activation with RLi (R = alkyl, aryl) and a silane, these complexes are known catalysts
for hydrosilylation reactions.
[0013] The following documents relate to hydrosilation of imines:
Ojima et al: "A novel method for the reduction of Schiff bases using catalytic hydrosilylation",
Tetrahedron Letters, 1 January 1973, p. 2475-1478.
US6072085
Lovel et al: "Hydrosilylation of heterocyclic aldimines catalysed by transition metal
complexes", Chemistry of Heterocyclic Compounds, 1 January 2002, p. 46-53.
Field et al: "Iridium (I)-catalysed tandem hydrosilylation-protodesilylation of imines",
European Journal of Organic Chemistry, vol. 2005, no. 14, 1 July 2005, p. 2881-2883.
Castro et al: "NHC-carbene cyclopentadienyl iron based catalyst for a general and
efficient hydrosilylation of imines", Chemical Communications, vol. 48, no. 1, 1 January
2012, p. 151-153.
Hashimoto et al: "Stoichiometric hydrosilylation of nitriles and catalytic hydrisilylation
of imines and ketones using a mu-silane diruthenium complex", Organometallics, ACS,
vol. 22, no. 11, 26 May 2003, p. 2199-2201.
FR2833944
Intemann: "Magnesium and zinc hydride complexes: From fundamental investigations to
potential applications in hydrogen storage and catalysis", PhD Thesis, 14 February
2014, p. 1-275
Harder et al: "From limestone to catalysis: Application of calcium compounds as homogeneous
catalysts", Chemical Reviews, vol. 110, no. 7, 14 July 2010, p. 3852-3876.
[0014] The following documents disclose organoaminosilanes:
CAS Database Accession No. 1965:446348 Sladkova T. A. et al. (1-methyl-1-n-butylamine-silacyclopentane).
CAS Database Accession No. 1973:477605 Andrianov K. A. et al. (1,1-diphenyl-N,N'-bis(silacyclobut-1-yl)silanediamine).
CAS Database Accession No. 1980:531604 Krapivin A. M. et al. (1-diethylamino-1-methyl-silacyclopentane).
EP2860182
[0015] The prior art synthesis reactions described above suffer from various deficiencies.
For example, in the synthesis routes that do not use a catalyst, the synthesis of
organoaminosilanes require multiple steps using, for example, (a) arylsilane, triflic
acid, secondary amine, and tertiary amine, (b) silylhalogen, excess secondary amine,
and metal hydride, or (c) silylhalogen, alkali metal amide, and metal hydride. Each
of these synthesis routes requires significant cooling to manage highly exothermic
reactions and produces significant amounts of salt byproducts that must be subsequently
removed by a filtration process.
[0016] Alternatively, the synthesis reactions described above that do involve catalytic
hydrosilylation of imines, are generally used for the synthesis of secondary amines
or, alternatively, for highlighting fundamentally unique catalysts. As such, the aforementioned
references do not describe a method for the synthesis, isolation, and purification
of organoaminosilanes to be used, for example, as precursors for the deposition of
silicon-containing films. It should be noted further that there are no description
in the above references wherein, silicon-containing sources such as silane (SiH
4), disilane (Si
2H
6), or methylsilane (MeSiH
3) gas are used as the Si-H starting material or silicon source material for the catalytic
hydrosilylation of imines to form organoaminosilane or organoaminodisilane compounds,
such as, for example, di-iso-propylaminosilane (DIPAS), di-iso-propylaminodisilane
(DIPADS), and di-iso-propylaminomethylsilane. Furthermore, there is no prior art that
teaches the use of complexes of alkaline earth metals such as Ca, Sr, Ba, which are
more abundant and less expensive than many transition metals, as catalysts for the
hydrosilylation of imines, whether it be for the synthesis of organoaminosilanes,
organoaminodisilanes, and organoaminocarbosilanes or the synthesis of organoamines.
[0017] Accordingly there is a need to provide a method of making compounds such as, without
limitation, organoamines, organoaminosilanes (e.g., DIPAS), organoaminodisilanes (e.g.,
DIPADS), and organoaminocarbosilanes, using commercially available reagents in relatively
high yields via the catalytic hydrosilylation of imines. There is also a need to provide
a method of making organoaminosilanes, such as without limitation, DIPAS, by a means
that eliminates or facilitates the separation of the product from reaction mixture.
There is a need to provide methods of making organoaminosilanes and/or organoamines
that reduces the overall production costs by reducing the costs of reagents used and/or
reducing agents. There is a need to provide a method of making organoaminosilanes
and/or organoamines that eliminates hazards associated with highly exothermic reactions
such as those involving triflic acid, metal amide, and metal hydride reagents. There
is a need to provide a method of making organoaminosilanes and/or organoamines that
avoids using halosilane starting materials, such that there are reduced halide impurities
in the purified product in order to avoid potential halides contamination if the compound
is used as a precursor for depositing silicon-containing films. There is also a need
for synthesis of compounds such as, without limitation, organoamines, organoaminosilanes,
organoaminodisilanes, or organoaminocarbosilanes via hydrosilylation of imines using
cheaper, more earth abundant metal catalysts compared to the currently widely used
precious metal (Ru, Rh, Ir, Pd, and Pt) catalysts.
BRIEF SUMMARY OF THE INVENTION
[0018] Described herein is a method for making compounds, more specifically organoaminosilanes,
organoaminodisilanes, organoaminocarbosilanes and/or organoamines, which provides
one or more of the following advantages over prior art methods to make such compounds:
(a) avoids the use of chlorosilane reagents which could lead to chlorine impurities
in the end product thereby eliminating chloride contamination when the end product
is being used as precursors to deposit a silicon containing film; (b) avoids the need
for additional filtration steps to remove amine-hydrochloride or alkali metal salt
byproducts which are common in prior art methods, and/or (c) avoids the use of pyrophoric
alkyllithium, metal hydride reagents, or extremely corrosive reagents such as triflic
acid. In this regard, the methods described herein improve upon the prior art methods
for making compounds such as organoaminosilanes, organoaminodisilanes, organoaminocarbosilanes,
and organoamines in one or more of the following ways: provides increased product
purity, improves the yield of end product, and/or avoids potential environmental health
and safety issues. The term "organoaminosilane" as used herein means a compound that
includes at least one N atom, at least one carbon-containing group, and at least one
Si atom and includes, without limitation, organoaminosilanes, organoaminodisilanes,
and organoaminocarbosilanes.
[0019] In one aspect, there is provided a method in accordance with Claim 1.
[0020] In another aspect, there is provided a method in accordance with claim 7. In certain
embodiments, the proton source is selected from the group consisting of water, alcohol,
or Brønsted acid.
DETAILED DESCRIPTION OF THE INVENTION
[0021] Methods for preparing compounds such as organoaminosilanes, organoaminodisilanes,
organoaminocarbosilanes, and organoamines are described herein using an imine having
a formula R-N=CR'R" wherein R, R' and R" are each independently selected from hydrogen,
a C
1-
10 linear alkyl group, a C
3-10 branched alkyl group, a C
3-10 cyclic alkyl group, a C
2-10 alkenyl group, a C
4-10 aromatic group, a C
4-10 heterocyclic group, a C
1-
10 linear organoamino group, a C
2-
10 branched organoamino group, a silyl group, a C
1-
10 linear carbosilyl group, and a C
2-
10 branched carbosilyl group and wherein R' and R" or R and R' can be linked to form
a substituted or an unsubstituted cyclic ring. In certain embodiments of the imine
having formula R-N=CR'R", R' and R" or R and R' in the formula are linked to form
the substituted or unsubstituted cyclic ring. In these embodiments, the imine can
be synthesized by condensing a primary amine having the formula RNH
2, with a ketone or aldehyde having the formula R'R"C=O. In alternative embodiments
of the imine having formula R-N=CR'R", R' and R" or R and R' in the formula are not
linked to form the substituted or unsubstituted cyclic ring.
[0022] In the formulas above and throughout the description, the term "alkyl" denotes a
linear or branched functional group having from 1 to 10 or from 3 to 10 carbon atoms,
respectively. Exemplary linear alkyl groups include, but are not limited to, methyl,
ethyl, n-propyl, n-butyl, n-pentyl, and hexyl. Exemplary branched alkyl groups include,
but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl,
isohexyl, and neohexyl. In certain embodiments, the alkyl group may have one or more
functional groups such as, but not limited to, an alkoxy group, a dialkylamino group,
an carbosilyl group, or combinations thereof, attached thereto. In other embodiments,
the alkyl group does not have one or more functional groups attached thereto.
[0023] In the formulas above and throughout the description, the term "cyclic alkyl" denotes
a cyclic functional group having from 3 to 10 or from 4 to 10 carbon atoms. Exemplary
cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl,
and cyclooctyl groups.
[0024] In the formulas above and throughout the description, the term "aryl" denotes an
aromatic cyclic functional group having from 5 to 10 carbon atoms. Exemplary aryl
groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.
In some embodiments, the aromatic cyclic group can have other elements such as oxygen,
or nitrogen. Exemplary such groups include, but not limited to, pyrrolyl, furanyl,
pyridinyl, pyridazinyl.
[0025] In the formulas above and throughout the description, the term "alkenyl group" denotes
a group which has one or more carbon-carbon double bonds and has from 2 to 10 or from
2 to 6 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl
or allyl groups.
[0026] In the formulas above and throughout the description, the term "alkynyl group" denotes
a group which has one or more carbon-carbon triple bonds and has from 2 to 10 or from
2 to 6 carbon atoms.
[0027] In the formulas above and throughout the description, the term "carbosilane" denotes
an organosilane comprising carbon, hydrogen, and silicon having from 1 to 10 carbon
atoms and from 1 to 10 silicon atoms, and which contains at least one Si-C bond. Examples
of carbosilanes include, without limitation, methylsilane, ethylsilane, diethylsilane,
dimethylsilane, triethylsilane, 1,2-dimethyldisilane,1,4-disilabutane, 2-methyl-1,3-disilapropane,
1,3-disilapropane, 1-silacyclopentane, 1-methyl-1-silacyclopentane, 1-silacyclobutane,
1,3-disilacyclobutane, and phenylsilane.
[0028] In the formulas above and throughout the description, the term "carbosilyl" denotes
an organosilyl group comprising carbon, hydrogen, and silicon having from 1 to 10
carbon atoms and from 1 to 10 silicon atoms, and which contains at least one Si-C
bond. Examples of carbosilyl groups include, without limitation, methylsilyl (-SiMeH
2), ethylsilyl (-SiEtH
2), diethylsilyl (-SiEt
2H), dimethylsilyl (-SiMe
2H), triethylsilyl (-SiEt
3), trimethylsilyl (-SiMe
3), 1,2-dimethyldisilyl(-SiMeHSiMeH
2),1,4-disilabutyl(-SiH
2CH
2CH
2SiH
3), dimethylvinylsilyl(-SiMe
2CH=CH
2), and phenylsilyl (-SiPhH
2).
[0029] In the formulas above and throughout the description, the term "silyl" denotes the
unsubstituted silyl group (-SiH
3).
[0030] In formulas above and throughout the description, the term "organoamino" denotes
a dialkylamino, alkylamino, or arylalkylamino group which may have from 1 to 10, or
from 1 to 4 carbon atoms. Exemplary organoamino groups include, but are not limited
to, dimethylamino (Me
2N-), diethylamino (Et
2N-), di-iso-propylamino (
iPr
2N-), iso-propyl-sec-butylamino, N-sec-butyl-N-iso-propylamino, N-ethyl-N-cyclohexylamino,
N-phenyl-N-iso-propylamino, tert-butylamino ('BuNH-), tert-pentylamino ('AmNH-), n-propylamino
(
nPrNH-), and iso-propylamino (
iPrNH-).
[0031] In certain embodiments of the formulas described herein, a substituent such as a
cyclic ring may be substituted or have one or more atoms or group of atoms substituted
in place of, for example, a hydrogen atom. Exemplary substituents include, but are
not limited to, oxygen, sulfur, halogen atoms (e.g., F, CI, I, or Br), nitrogen, and
phosphorous. In alternative embodiments, the substitutent is not unsubstituted.
[0032] The method described herein involves the catalytic hydrosilylation of imines as an
alternative route to the synthesis of compounds such as organoaminosilane, organoaminodisilane,
and organoaminocarbosilane which can be used, without limitation, as precursors in
the deposition of silicon-containing films. For example, in one embodiment, the organoaminosilane
iPr
2N-SiH
3 could be conveniently synthesized by reacting the imine N-iso-propyl-iso-propylidenimine
with a silicon source (hydridosilane) such as silane gas (SiH
4). In another embodiment, the organoaminodisilane
iPr
2N-SiH
2SiH
3 could be obtained in a similar fashion by reacting the imine N-iso-propyl-iso-propylidenimine
with a silicon source (hydridosilane) such as disilane gas (Si
2H
6). . In certain embodiments, asymmetric imines could be used as a reagent in a reaction
mixture comprising a silicon source (hydridosilane) in the presence of a catalyst
to provide organoaminosilanes, organoaminodisilanes, or organoaminocarbosilanes having
asymmetric organoamino groups. In this regard, these asymmetric organoamino precursors
would otherwise have been unfeasible to synthesize using prior art methods due to
scarcity of the corresponding amine [e.g. (
sBu)(
iPr)NH, (
tBu)(
iPr)NH].
[0033] The methods described herein provide a means to synthesize desirable compounds such
as but not limited to organoaminosilanes (e.g., DIPAS), organoaminodisilanes (e.g.,
DIPADS), organoaminocarbosilanes, at relatively high yields. In this regard, exemplary
yields obtainable for the compounds using the synthesis method described herein are
50 mol% or greater, 55 mol% or greater, 60 mol% or greater, 65 mol% or greater, 70
mol% or greater, 75 mol% or greater, 80 mol% or greater, or 90 mol% or greater based
on the imine usage. In synthesis processes wherein the silicon source comprises a
hydridosilane reagent having at least two Si-H groups, once one hydrosilylation has
taken place at a single silicon atom, the rate for a second, third, or fourth hydrosilylation
to take place at the same silicon atom becomes significantly and successively slower.
In contrast, in synthesis processes involving reacting lithium-amides with Si-X
n (X = halide or H, n = 2,3,4) compounds, or when reacting primary or secondary amines
with said compounds, preventing over-amination is difficult. Therefore, there is a
kinetic selectivity for preparing compounds such as organoaminosilanes in a more subtle,
less harsh hydrosilylation method such as the method described herein.
[0034] As previously discussed, an imine is reacted with a silicon source (hydridosilane)
to form a reaction mixture comprising a compound such as without limitation, an organoaminosilane
(e.g., DIPAS), an organoaminodisilanes (e.g., DIPADS), or an organoaminocarbosilane.
The hydridosilanes used in methods of the invention are defined in claim 1.
[0035] The imine reagents may include secondary aldimines, R-N=CHR', or secondary ketimines,
R-N=CR'R", containing linear or branched organic R, R' and R" functionalities and
wherein R, R' and R" are as described herein, though it is preferable that alkyl functionalities
be sufficiently large to afford stability during purification processes and storage
of the final organoaminosilane product. Exemplary imines include, but are not limited
to, N-iso-propyl-iso-propylidenimine, N-iso-propyl-sec-butylidenimine, N-sec-butyl-sec-butylidenimine,
and N-tert-butyl-iso-propylidineimine.
[0036] The molar ratio of imine to the hydridosilane in the reaction mixture ranges from
0.1:1 to 10:1. Exemplary ratios of imine to the hydridosilane include, but are not
limited to, 0.1:1, 1:1, 2:1, 3:1, 5:1, and 10:1. In embodiments wherein the hydridosilane
reagent in the reaction mixture comprises three or more Si-H bonds per silicon atom,
an excess of hydridosilane is used to avoid bis(amino)silane products. In one particular
embodiment, the reaction mixture has a 1:2.2 to 1:2.3 molar ratio of imine to hydridosilane
to ensure the reaction proceeds quickly to completion and to prevent more than one
hydrosilylation reaction per hydridosilane molecule.
[0037] The molar ratio of catalyst to imine in the reaction mixture ranges from 0.0000001:1
to 1:1. Exemplary ratios of catalyst to imine include, but are not limited to 0.1:1,
0.01:1, 0.05:1, 0.07:1, 0.005:1, 0.001:1, 0.0001:1, 0.0005:1, 0.00001:1, 0.00005:1,
and 0.00008:1. In one particular embodiment 0.05 to 0.07 equivalents of catalyst is
used per equivalent of imine. In another particular embodiment 0.00008 equivalents
of catalyst is used per equivalent of imine.
[0038] In certain embodiments, the reaction mixture comprising the hydridosilane reagent(s),
imine reagent(s), and catalyst(s) further comprises an anhydrous solvent. Exemplary
solvents may include, but are not limited to linear-, branched-, cyclic- or polyethers
(e.g., tetrahydrofuran (THF), diethyl ether, diglyme, and/or tetraglyme); linear-,
branched-, or cyclic- alkanes, alkenes, aromatics and halocarbons (e.g. pentane, hexanes,
toluene and dichloromethane). The selection of one or more solvent, if added, may
be influenced by its compatibility with reagents contained within the reaction mixture,
the solubility of the catalyst, and/or the separation process for the intermediate
product and/or the end product chosen. In other embodiments, the reaction mixture
does not comprise a solvent. In these or other embodiments, the mixture of imine and
hydridosilane reagents may be used as the liquid medium for the reaction in the reaction
mixture.
[0039] In the method described herein, the reaction between the hydridosilane reagent(s)
and the imine reagent(s) occurs at one or more temperatures ranging from 0°C to 100°C.
Exemplary temperatures for the reaction include ranges having any one or more of the
following endpoints: 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100°C. The suitable
temperature range for this reaction may be dictated by the physical properties of
the hydridosilane reagent(s), imine reagent(s), catalyst(s), and optional solvent.
Examples of particular reactor temperature ranges include but are not limited to,
0°C to 80°C or from 0°C to 30°C.
[0040] In certain embodiments of the method described herein, the pressure of the reaction
may range from 1 to 115 psia (7 to 790 kPa) or from 15 to 45 psia (100 to 310 kPa).
In some embodiments where the hydridosilane reagent is a liquid under ambient conditions,
the reaction is run at atmospheric pressure. In some embodiments where the hydridosilane
reagent is a gas under ambient conditions, the reaction is run at a pressure above
15 psia (100 kPa).
[0041] In certain embodiments, one or more reagents may be introduced to the reaction mixture
as a liquid or a vapor. In embodiments where one or more of the reagents is added
as a vapor, a non-reactive gas such as nitrogen or an inert gas may be employed as
a carrier gas to deliver the vapor to the reaction mixture. In embodiments where one
or more of the reagents is added as a liquid, the regent may be added neat, or alternatively
diluted with a solvent. The reagent is fed to the reaction mixture until the desired
conversion to the crude mixture containing the organoaminosilane product, or crude
liquid, has been achieved. In certain embodiments, the reaction may be run in a continuous
manner by replenishing the hydridosilane and/or imine reagents and removing the reaction
products and the crude liquid from the reactor.
[0042] An example of the catalytic hydrosilation method described herein comprises combining
a hydridosilane and an imine to provide a reaction mixture in the presence of 0.1-10
mol% catalyst under ambient conditions to produce an organoaminosilane, organoaminodisilane,
or organoaminocarbosilane compound as shown below in the following reaction scheme
(1). The hydridosilane reagent in accordance with the invention is defined in the
claims. In a general scheme the organosilane reagent has the following formula R
1R
2R
3SiH wherein R
1, R
2 and R
3 are each independently selected from hydrogen, C
1-
10 linear alkyl group, a C
3-10 branched alkyl group, a C
4-10 cyclic alkyl group, a C
2-10 alkenyl group, a C
4-10 aromatic group, a C
4-10 heterocyclic group, a C
1-
10 linear organoamino group, a C
2-10 branched organoamino groups, a silyl group, a C
1-
10 linear carbosilyl group, and a C
2-
10 branched carbosilyl group.
[0043] The reaction may require an excess of either hydridosilane reagent or imine to regulate
the extent of hydrosilylation, and solvents such as tetrahydrofuran (THF) or hexanes
may be used to facilitate the reaction progress. With hydridosilane reagents that
are volatile liquids or gases [e.g. SiH
4 (silane), Si
2H
6 (disilane), MeSiH
3 (methylsilane), PhSiH
3 (phenylsilane), H
3SiCH
2CH
2SiH
3 (1,4-disilabutane), H
3SiCH
2SiH
3 (1,3-disilapropane), H
3SiCH(CH
3)SiH
3 (2-methyl-1,3-disilapropane), pressures greater than 1 atmospheres (atm) may be required
to maintain sufficient levels of these reagents in the liquid phase. Once the reaction
is complete or has reached equilibrium, the organoaminosilane, organoaminodisilane,
or organoaminocarbosilane product can be purified by distillation. Referring to the
above reaction scheme (1), the final organoaminosilane, organoaminodisilane, or organoaminocarbosilane
product is formed by the reaction of the imine and hydridosilane. A >50% stoichiometric
excess of hydridosilane is generally used to ensure complete reaction, though smaller
excesses may be used if the mixing period is adequately long.
[0044] The crude mixture comprising the desired organoaminosilane, organoaminodisilane,
or organoaminocarbosilane product, catalyst(s), and potentially residual imine, residual
hydridosilane, solvent(s), or undesired organoaminosilane product(s) may require separation
process(es). Examples of suitable separation processes include, but are not limited
to, distillation, evaporation, membrane separation, filtration, vapor phase transfer,
extraction, fractional distillation using an inverted column, and combinations thereof.
In particular embodiments, the crude fluid is first separated from the residual catalyst
by vacuum transfer or distillation at lower temperatures prior to isolation of the
desired product by fractional distillation in order to prevent the catalyzation of
undesired reactions during the purification process. In these embodiments, the pressure
can vary considerably from atmospheric to full vacuum. In this embodiment or other
embodiments, the reaction occurs at one or more temperatures ranging from 20°C to
200°C. Exemplary temperatures for the reaction include ranges having any one or more
of the following endpoints: 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140,
150, 160, 170, 180, 190, or 200°C. Examples of particular reactor temperature ranges
include but are not limited to, 20°C to 200°C or from 70°C to 160°C.
[0045] In certain embodiments of the method described herein, the pressure of the reaction
may range from 0.1 to 115 psia (0.7 to 790 kPa) or from 10 to 45 psia (70 to 310 kPa).
In one particular embodiment, the reaction is run at a pressure of about 100 psia
(about 700 kPa).
[0046] In certain preferred embodiments, the reagents in the reaction mixture are gaseous.
In these embodiments, the contact of the catalyst with reaction mixture may be defined
in terms of defined by the bulk reactor volume displaced by the catalyst ÷ reactant
(e.g., silane and/or silicon source gas) gas flow rate. The gas-catalyst contact time
may range from 5 to 200 seconds. Exemplary times for the contact of the reactive mixture
with the catalyst include ranges having any one or more of the following endpoints:
5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180,
190, or 200 seconds. Examples of particular contact time ranges include but are not
limited to, 20 to 100 or from 10 to 40 seconds.
[0047] Exemplary catalysts that can be used with the method described herein include, but
are not limited to the following: alkaline earth metal catalysts; halide-free main
group, transition metal, lanthanide, and actinide catalysts; and halide-containing
main group, transition metal, lanthanide, and actinide catalysts.
[0048] Exemplary alkaline earth metal catalysts include but are not limited to the following:
Mg[N(SiMe
3)
2]
2, To
MMgMe [To
M =tris(4,4-dimethyl-2-oxazolinyl)phenylborate], To
MMg-H, To
MMg-NR
2 (R = H, alkyl, aryl) Ca[N(SiMe
3)
2]
2, [(dipp-nacnac)CaX(THF)]
2 (dipp-nacnac = CH[(Cme)(2,6-
iPr
2-C
6H
3N)]
2; X = H, alkyl, carbosilyl, organoamino), Ca(CH
2Ph)
2, Ca(C
3H
5)
2, Ca(α-Me
3Si-2-(Me
2N)-benzyl)
2(THF)
2, Ca(9-(Me
3Si)-fluorenyl)(α-Me3Si-2-(Me2N)-benzyl)(THF), [(Me
3TACD)
3Ca
3(
µ3-H)
2]
+ (Me3TACD = Me
3[12]aneN
4), Ca(
η2-Ph
2CNPh)(hmpa)
3 (hmpa = hexamethylphosphoramide), Sr[N(SiMe
3)
2]
2, and other M
2+ alkaline earth metal-amide, -imine, -alkyl, -hydride, and -carbosilyl complexes (M
= Ca, Mg, Sr, Ba).
[0049] Exemplary halide-free, main group, transition metal, lanthanide, and actinide catalysts
include but are not limited to the following: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene,
2,2'-bipyridyl, phenanthroline, B(C
6F
5)
3, BR
3 (R = linear, branched, or cyclic C
1 to C
10 alkyl group, a C
5 to C
10 aryl group, or a C
1 to C
10 alkoxy group), AIR
3 (R = linear, branched, or cyclic C
1 to C
10 alkyl group, a C
5 to C
10 aryl group, or a C
1 to C
10 alkoxy group), (C
5H
5)
2TiR
2 (R = alkyl, H, alkoxy, organoamino, carbosilyl), (C
5H
5)
2Ti(Oar)
2 [Ar = (2,6-(
iPr)
2C
6H
3)], (C
5H
5)
2Ti(SiHRR')Pme
3 (wherein R, R' are each independently selected from H, Me, Ph), TiMe
2(dmpe)
2 (dmpe = 1,2-bis(dimethylphosphino)ethane), bis(benzene)chromium(0), Cr(CO)
6, Mn
2(CO)
12, Fe(CO)
5, Fe
3(CO)
12, (C
5H
5)Fe(CO)
2Me, Co
2(CO)
8, Ni(ll) acetate, Nickel(II) acetylacetonate, Ni(cyclooctadiene)
2, [(dippe)Ni(µ-H)]
2 (dippe = 1,2-bis(diisopropylphosphino)ethane), (R-indenyl)Ni(PR'
3)Me (R = 1-
iPr, 1-SiMe
3, 1,3-(SiMe3)2; R' = Me,Ph), [{Ni(
η-CH
2:CHSiMe
2)
2O}
2{
µ-(
η-CH
2:CHSiMe
2)
2O}], Cu(I) acetate, CuH, [tris(4,4-dimethyl-2-oxazolinyl)phenylborate]ZnH, (C
5H
5)
2ZrR
2 (R = alkyl, H, alkoxy, organoamino, carbosilyl), Ru
3(CO)
12, [(Et
3P)Ru(2,6-dimesitylthiophenolate)][B[3,5-(CF
3)
2C
6H
3]
4], [(C
5Me
5)Ru(R
3P)
x(NCMe)
3-x]
+ (wherein R is selected from a linear, branched, or cyclic C
1 to C
10 alkyl group and a C
5 to C
10 aryl group; x = 0, 1, 2, 3), Rh
6(CO)
16, tris(triphenylphosphine)rhodium(I)carbonyl hydride, Rh
2H
2(CO)
2(dppm)
2 (dppm = bis(diphenylphosphino)methane, Rh
2(
µ-SiRH)
2(CO)
2(dppm)
2 (R = Ph, Et, C
6H
13), Pd/C, tris(dibenzylideneacetone)dipalladium(0), tetrakis(triphenylphosphine)palladium(0),
Pd(II) acetate, (C
5H
5)
2SmH, (C
5Me
5)
2SmH, (THF)
2Yb[N(SiMe
3)
2]
2, (NHC)Yb(N(SiMe
3)
2)
2 [NHC = 1,3-bis(2,4,6-trimethylphenyl) etrahydr-2-ylidene)], Yb(
η2-Ph
2CNPh)(hmpa)
3 (hmpa = hexamethylphosphoramide), W(CO)
6, Re
2(CO)
10, Os
3(CO)
12, Ir
4(CO)
12, (acetylacetonato)dicarbonyliridium(I), Ir(Me)
2(C
5Me
5)L (L = Pme
3, PPh
3), [Ir(cyclooctadiene)Ome]
2, PtO
2 (Adams's catalyst), Pt/C, Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's
catalyst), bis(tri-
tert-butylphosphine)platinum(0), Pt(cyclooctadiene)
2, [(Me
3Si)
2N]
3U][BPh
4], [(Et
2N)
3U][BPh
4], and other halide-free M
n+ complexes (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd,
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir,
Pt, U; n = 0, 1, 2, 3, 4, 5, 6).
[0050] Exemplary halide-containing, main group, transition metal, lanthanide, and actinide
catalysts include but are not limited to the following: BX
3 (X = F, Cl, Br, I), BF
3•Oet
2, AlX
3 (X = F, Cl, Br, I), (C
5H
5)
2TiX
2 (X = F, Cl), [Mn(CO)
4Br]
2, NiCl
2, (C
5H
5)
2ZrX
2 (X = F, Cl), PdCl
2, PdI
2, CuCI, CuI, CuF
2, CuCl
2, CuBr
2, Cu(PPh
3)
3Cl, ZnCl
2, [(C
6H
6)RuX
2]
2 (X = Cl, Br, I), (Ph
3P)
3RhCl (Wilkinson's catalyst), [RhCl(cyclooctadiene)]
2, di-
µ-chloro-tetracarbonyldirhodium(I), bis(triphenylphosphine)rhodium(I) carbonyl chloride,
Ndl
2, SmI
2, DyI
2, (POCOP)IrHCl (POCOP = 2,6-(R
2PO)
2C
6H
3; R =
iPr,
nBu, Me), H
2PtCl
6•
nH
2O (Speier's catalyst), PtCl
2, Pt(PPh
3)
2Cl
2, and other halide-containing M
n+ complexes (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd,
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir,
Pt, U; n = 0, 1, 2, 3, 4, 5, 6).
[0051] In certain embodiments, the compounds, or organoaminosilanes, organoaminodisilanes,
and organoaminocarbosilanes, prepared using the methods described herein and compositions
comprising the compounds are preferably substantially free of halide ions. As used
herein, the term "substantially free" as it relates to halide ions (or halides) such
as, for example, chlorides and fluorides, bromides, and iodides, means less than 5
ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm,
and most preferably 0 ppm. Compositions that are substantially free of halides can
be achieved by (1) reducing or eliminating chloride sources during chemical synthesis,
and/or (2) implementing an effective purification process to remove chloride from
the crude product such that the final purified product is substantially free of halides.
Halide sources may be reduced during synthesis by using reagents that do not contain
halides such as the halide-free catalysts described herein. In a similar manner, the
synthesis should not use halide based solvents, catalysts, or solvents which contain
unacceptably high levels of halide contamination. Alternatively, or additionally,
the crude product may also be treated by various purification methods to render the
final product substantially free of halides such as chlorides. Such methods are well
described in the prior art and, may include, but are not limited to, purification
processes such as distillation, or adsorption. Distillation is commonly used to separate
impurities from the desire product by exploiting differences in boiling point. Adsorption
may also be used to take advantage of the differential adsorptive properties of the
components to effect separation such that the final product is substantially free
of halide. Adsorbents such as, for example, commercially available solid bases can
be used to remove halides such as chloride.
[0055] Table 8 is deleted.
[0057] In another embodiment of the method described herein, the compound selected from
organoaminosilane, organoaminodisilane, or organoaminocarbosilane is reacted with
a proton source to provide an organoamine. In this embodiment, the step, of reacting
the compound with a proton source, could be performed prior to or after the purification
of the compound. The reagents could be combined neat or, alternatively in the presence
of a solvent (e.g., at least one of the proton source or the compound is dissolved
in solvent). An excess of proton source can be used to drive the reaction to completion,
aid in the purification process, or both. Alternatively, a slight deficiency of the
proton source can be used to eliminate the need of separating unreacted proton source
from the organoamine product. In one particular embodiment, the proton source is delivered
as a vapor into the reaction solution comprising the organoaminosilane. The protonation
step (e.g., reaction of the proton source with the compound) could be performed in
the temperature range between -50°C to 150°C for the addition of reagents and/or for
the extent of the reaction. In some embodiments, the protonation step may be carried
out at lower temperature (below 0 °C) in order to help remove heat and prevent side
reactions. In other embodiments, higher temperatures (above 30 °C) may be preferred
to drive the intended protonation reaction to completion. Reaction times could range
from 5 minutes to 30 minutes, to 1 h, to 6h, to 12 h, to 24 hr or more. The protonation
reaction mixture may likely yield more than one phase (liquid-liquid or liquid-solid)
which can be separated by filtration, decantation, separator funnel, distillation,
adsorption, centrifugation, or other means. Purification of the end organoamine product
may be accomplished by distillation, column chromatography, gas chromatography, sublimation,
crystallization, or other purification processes.
[0058] The following examples illustrate the method described herein for preparing compounds
such as, without limitation organoaminosilanes, organoaminodisilanes, organoaminocarbosilanes,
and is not intended to limit it in any way.
EXAMPLES
[0059] For the following examples, gas chromatography (GC-TCD), mass spectrometry (GC-MS),
and
1H NMR spectroscopy were used to identify and quantify the solution compositions as
appropriate. Gas chromatographic analyses were carried out on the product effluent
using a TCD equipped HP-5890 Series II GC and a 0.53mm diameter x 30m Supleco column
containing 3µm thick SPB-5 media. Chloride analyses were performed by hydrolyzing
the sample with water at 85 °C and injecting the liquid phase into a Metrohm Ion Chromatography
instrument equipped with a conductivity detector.
EXAMPLE 1: Synthesis of N,N-di-iso-propylaminosilane (cf. Table 2)
[0060] The catalyst Ru
3(CO)
12 (0.10 g, 0.16 mmol) was dissolved in the imine N-iso-propylidene-iso-propylamine
(7.0 g, 71 mmol) and the resulting solution was exposed to a silicon source gas (SiH
4) at 82 psia (575 kPa) for 6 hours at 40 °C. The resulting reaction solution was determined
by GC-MS to contain N,N-di-iso-propylaminosilane. GC-MS showed the following peaks:
131 (M+), 126 (M-15), 116, 110, 98, 88, 74.
EXAMPLE 2: Synthesis of N,N-di-iso-propylaminodisilane (cf. Table 3)
[0061] The catalyst Ru
3(CO)
12 (0.10 g, 0.16 mmol) was dissolved in the imine N-iso-propylidene-sec-butylamine (7.0
g, 71 mmol) and the resulting solution was exposed to a disilane gas (Si
2H
6) at 102 psia (703 kPa) for 6 hours at 40 °C. The reaction solution was determined
by GC-MS to contain N,N-di-iso-propylaminodisilane. GC-MS showed the following peaks:
161 (M+), 146 (M-15), 128, 114, 104, 88, 72.
EXAMPLE 3: Synthesis of 1-(N,N-di-iso-propylamino)-1,4-disilabutane (cf. Table 5)
[0062] A mixture of a silicon source, 1,4-disilabutane (0.48 g, 5.3 mmol), and the imine
N-iso-propylidene-iso-propylamine (0.25 g, 2.5 mmol) was added to a stirred suspension
of the catalyst, anhydrous NiCl
2 (0.02 g, 0.15 mmol), in etrahydrofuran (THF) (1 mL), in a nitrogen-filled glovebox.
After 2 days of stirring at room temperature, the resulting brown mixture was filtered
to remove catalyst sediments and was determined by GC and GC-MS to contain the end
product 1-(N,N-di-iso-propylamino)-1,4-disilabutane. GC-MS showed the following peaks:
189 (M+), 188 (M-1), 174 (M-15), 159, 144, 130, 102.
EXAMPLE 4: Synthesis of 1-(N,N-di-sec-butylamino)-1,4-disilabutane (cf. Table 5)
[0063] A mixture of a silicon source, 1,4-disilabutane (0.50 g, 5.54 mmol), and the imine
N-sec-butylidene-sec-butylamine (0.35 g, 2.75 mmol) was added to a stirred solution
of the catalyst (Ph
3P)
3RhCl (0.02 g, 0.02 mmol) in THF (0.5 mL). After 1 day of stirring, the imine was completely
consumed, and the resulting orange solution was determined by GC and GC-MS to contain
the end product 1-(N,N-di-sec-butylamino)-1,4-disilabutane. GC-MS showed the following
peaks: 217 (M+), 202 (M-15), 189, 172, 158, 144, 132, 114, 102.
EXAMPLE 5: Synthesis of 1-(N-sec-butyl-N-iso-propylamino)-1,4-disilabutane (cf. Table
5)
[0064] A mixture of a silicon source, 1,4-disilabutane (0.50 g, 5.54 mmol), and the imine
N-sec-butylidene-iso-propylamine (0.32 g, 2.83 mmol) was added to a stirred solution
of the catalyst (Ph
3P)
3RhCl (0.02 g, 0.02 mmol) in THF (0.5 mL). After 1 day of stirring, the imine was completely
consumed, and the resulting orange solution was determined by GC and GC-MS to contain
the end product 1-(N-sec-butyl-N-iso-propylamino)-1,4-disilabutane. GC-MS showed the
following peaks: 203 (M+), 188 (M-15), 174, 158, 144, 130, 119, 102.
EXAMPLE 6: Synthesis of 1-(N,N-di-iso-propylamino)-1-methyl-silacyclopentane (comparative
example)
[0065] The solid catalyst Ca[N(SiMe
3)
2]
2 (0.01 g, 0.03 mmol) was added to a mixture of a silicon source, 1-methyl-1-silacyclopentane
(0.15 g, 1.5 mmol), and the imine N-iso-propylidene-iso-propylamine (0.15 g, 1.5 mmol).
After 2 weeks, the pale yellow reaction solution was determined by GC and GC-MS to
contain 1-(N,N-di-iso-propylamino)-1-methyl-1-silacyclopentane as the major product.
GC-MS showed the following peaks: 199 (M+), 179, 164, 148, 134, 122, 107, 91, 81,
77.
EXAMPLE 7: Synthesis of N,N-di-iso-propylamino-phenylsilane (cf. Table 17, comparative
example)
[0066] A solution of the catalyst (Ph
3P)
3RhCl (0.01 g, 0.01 mmol) in THF (1 mL) was added to a stirred solution of a silicon
source, phenylsilane (0.30 g, 2.77 mmol), and the imine N-iso-propylidene-iso-propylamine
(0.12 g, 1.21 mmol). After 1 day of stirring, the imine was almost completely consumed,
and the resulting orange solution was determined by GC and GC-MS to contain N,N-di-iso-propylamino-phenylsilane
as the major product. GC-MS showed the following corresponding peaks: 207 (M+), 192
(M-15), 177, 164, 150, 134, 121, 107, 86, 72. Minor products observed include N,N-di-iso-propylaminosilane,
bis(N,N-di-iso-propylamino)silane, and diphenylsilane.
Comparative EXAMPLE 1: Synthesis of N,N-di-n-propylaminodiethylsilane using chlorosilane
[0067] Traditional method to make organoaminocarbosilane: Chlorodiethysilane (18.5 g, 151
mmol) was added dropwise to a stirred solution of di-n-propylamine (32.1 g, 317 mmol)
in hexanes (250 mL) at -15 °C. The resulting white slurry was allowed to warm to room
temperature while stirring. The white solids were removed by filtration and the colorless
filtrate was purified by vacuum distillation to obtain 22.2 g of N,N-di-n-propylaminodiethylsilane.
GC-MS showed the following peaks: 187 (M+), 172 (M-15), 158, 144, 130, 116, 100, 87,
72. This product was determined after hydrolysis to contain 537 ppm chloride.
EXAMPLE 8: Synthesis of N,N-di-n-propylaminodiethylsilane (comparative)
[0068] Method to make organoaminocarbosilane: A solution of the catalyst (Ph
3P)
3RhCl (0.40 mL, 0.029 M, 0.012 mmol) in THF was added to a stirred solution of a silicon
source, diethylsilane (14.6 g, 165 mmol), and the imine N-n-propylidene-n-propylamine
(14.4 g, 145 mmol). After 3 days of stirring, the reaction solution was purified by
vacuum distillation to obtain 21.4 g of N,N-di-n-propylaminodiethylsilane. This product
was determined after hydrolysis to contain 22 ppm chloride, demonstrating the hydrosilylation
route provides much less chloride contamination than the route employing chlorosilanes
as starting material. Furthermore, the chloride (or other halide) content can be reduced
to non-detectable if halide-free catalysts are being employed in the hydrosilylation.
Examples 9-21: Synthesis of additional organoaminosilane, organoaminodisilane, or
organoaminocarbosilane compounds.
[0069] Additional organoaminosilanes, organoaminodisilanes, and organoaminocarbosilanes
were made via similar fashion as Examples 1 to 8 and were characterized by GC-MS.
The molecular weight (MW), the structure, and corresponding major MS fragmentation
peaks of each compound are provided in Table 18 to confirm their identification.
Table 18. Organoaminosilane, organoaminodisilane, or organoaminocarbosilane compounds
synthesized via hydrosilylation of imines.
Ex. |
Precursor Name |
MW |
Structure |
MS Peaks |
9 |
N-sec-butyl-N-iso-propylaminosilane (cf. Table 2) |
145.32 |
|
145, 130, 116, 100, 88, 74 |
10 |
N,N-di-sec-butylaminosilane (cf. Table 2) |
159.35 |
|
159, 144, 130, 114, 100, 88, 74, |
11 |
N-sec-butyl-N-iso-propylaminodisilane (cf. Table 3) |
175.42 |
|
175, 160, 146, 128, 114, 104, 86, 72 |
12 |
N,N-di-sec-butylaminosilane (cf. Table 3) |
189.45 |
|
189, 174, 160, 142, 128, 118, 104, 86, 72 |
13 |
1,2-bis(N,N-di-iso-propylamino)disilane (comparative example) |
260.57 |
|
260, 245, 229, 215, 187, 173, 158, 144, 128, 116, 100, 86 |
14 |
1,2-bis(N-sec-butyl-N-iso-propylamino)disilane (comparative example) |
288.63 |
|
288, 273, 259, 172, 158, 144, 130, 116, 100, 86, 72 |
15 |
1-(N-n-propyl-N-iso-propylamino)-1,4-disilabutane (cf. Table 5) |
189.45 |
|
189, 174, 160, 144, 130, 116, 102, 86 |
16 |
1,4-bis(N-n-propyl-N-iso-propylamino)-1,4-disilabutane (comparative example) |
288.63 |
|
288, 274, 260, 244, 230, 216, 201, 188, 173, 160, 144, 128 |
17 |
1,4-bis(N,N-di-iso-propylamino)-1,4-disilabutane (comparative example) |
288.63 |
|
288, 287, 243, 229, 207, 188, 144, 130 |
18 |
1,4-bis(N-sec-butyl-N-iso-propylamino)-1,4-disilabutane (comparative example) |
316.68 |
|
316, 301, 281, 257, 243, 229, 215, 202, 186, 172, 158 |
19 |
1-(N,N-di-iso-propylamino)-silacyclopentane (comparative example) |
185.39 |
|
185, 170, 154, 142, 128, 112, 99, 85, 70 |
20 |
1-(N,N-di-iso-propylamino)-1,3-disilacyclobutane (comparative example) |
187.43 |
|
187, 172, 159, 143, 130, 115, 101, 86, 73 |
21 |
1,3-bis(N,N-di-iso-propylamino)-1,3-disilacyclobutane (comparative example) |
286.61 |
|
286, 271, 243, 229, 213, 186, 172, 144, 128, 101, 87, 70 |